Thiochalcone substituted phthalocyanines for dye-sensitized solar cells: Relation of optical and electrochemical properties for cell performance

The new peripherally tetra-substituted metallophthalocyanines (MPcs, M=Zn, Co, Ni) bearing the chalcone, (E)-3-(4-hydroxyphenyl)-1-(thiophen-2-yl)prop-2-en-1-one, for dye-sensitized solar cells (DSSCs) were synthesized. FT-IR, ¹H NMR, ¹³C NMR, and UV–Vis spectroscopy techniques were utilized for characterization of all the MPcs. Electrochemical, optical and photovoltaic properties of all the MPcs as sensitizers were examined. Electrochemical studies reveal that while the ZnPc (4) and NiPc (6) give only Pc ring-based redox reactions, the CoPc (5) shows redox reactions based on both the central metal and the ring due to the metal 3d orbitals lying between the Pc HOMO and LUMO. The DSSC based on 5 gave the lowest power conversion efficiency (0.51%), perhaps due to the presence of a redox active central metal ion in the core of the complex, which results in a decrease electron transfer in the device. However, cells based on the other complexes including redox inactive central metal ions, which cannot reduce electron transfer, showed reasonable power conversion efficiencies of 1.27% and 1.11% for 4 and 6, respectively. The slight difference between the efficiencies can be attributed to higher molar extinction coefficient and narrower band gap of 4 than 6, which ensure a higher photocurrent and broader light absorption in the visible region.     

New β-isatin aldehyde-N,N′-thiocarbohydrazones: preparation,spectroscopic studies and DFT approach to antioxidant characteristics

Research on Chemical Intermediates - Five new Schiff bases of isatin and its derivatives were prepared from monothiocarbohydrazides and 5-chloro isatin. The chemical structures of the synthesized...     

Charge state of the fast gate in chloride channels: insights from electrostatic calculations in a schematic model

Fast gating is a unique property of chloride channels, where a permeating Cl(-) ion acts as its own ligand in opening the channel. The glutamate residue implicated in fast gating normally carries a unit negative charge. Whether this charge needs to be protonated to enable permeation of a Cl(-) ion is an important question that will affect how models of chloride channels are constructed. We investigate the energetic consequences of the charge state of this glutamate residue from continuum electrostatics using a schematic cylindrical channel model. Both analytical solutions of the Poisson equation for an infinite cylinder and numerical ones for a finite cylinder are employed in the calculations.     

A combined experimental and theoretical study on 8-hydroxy-2-quinolinecarboxylic acid

The mid-IR and Raman spectra of 8-hydroxy-2-quinolinecarboxylic acid (8HQC) were recorded. These spectra were interpreted with the help of B3LYP/6–311 ++G(d,p) calculations and potential energy distribution (PED) analysis. As a result of the calculations, seven tautomers were determined among many stable conformations. The experimental spectra were concordant with the theoretical data of one tautomer. In the functional group region overtone and combination bands were detected and assigned. In addition, because of several peaks in the IR spectrum, it was proposed that the 8HQC exhibits dimerization in condensed phase. Possible dimeric forms of 8HQC were evaluated at the same level of theory, and it has been seen that the calculation results confirm the above proposal. ¹H and ¹³C NMR chemical shifts of 8HQC have been calculated, and compared with the experimental data. The frontier molecular orbital properties and the atomic charges were also theoretically obtained and presented.     

Design and implementation of fuzzy logic based automatic gain controller for EDFAs

In this study, the design and implementation of a fuzzy logic (FL) based automatic gain controller card (AGC) is performed in order to control the pump laser current with respect to signal power and signal wavelength. The FL-AGC card consists of an amplifier, an analogue to digital converter (ADC), a digital to analogue converter (DAC), and a FL based software that is embedded to a microcontroller. With this configuration, gain flattening at the output of the erbium doped fibre amplifier (EDFA) along C band is achieved. In this way, ergonomically designed FL-AGC card can be easily matched with EDFAs and can be applicable to optical system applications.     

Value of supplier’s capacity information in a two-echelon supply chain

In traditional supply chain models it is generally assumed that full information is available to all parties involved. Although this seems reasonable, there are cases where chain members are independent agents and possess different levels of information. In this study, we analyze a two-echelon, single supplier-multiple retailers supply chain in a single-period setting where the capacity of the supplier is limited. Embedding the lack of information about the capacity of the supplier in the model, we aim to analyze the reaction of the retailers, compare it with the full-information case, and assess the value of information and the effects of information asymmetry using game theoretic analysis. In our numerical studies, we conclude that the value of information is highly dependent on the capacity conditions and estimates of the retailers, and having information is not necessarily beneficial to the retailers.     

Coupled thermoviscoplasticity of glassy polymers in the logarithmic strain space based on the free volume theory

The paper outlines a constitutive model for finite thermo-visco-plastic behavior of amorphous glassy polymers and considers details of its numerical implementation. In contrast to existing kinematical approaches to finite plasticity of glassy polymers, the formulation applies a plastic metric theory based on an additive split of Lagrangian Hencky-type strains into elastic and plastic parts. The analogy between the proposed formulation in the logarithmic strain space and the geometrically linear theory of plasticity, makes this constitutive framework very transparent and attractive with regard to its numerical formulation. The characteristic strain hardening of the model is derived from a polymer network model. We consider the particularly simple eight chain model, but also comment on the recently developed microsphere model. The viscoplastic flow rule in the logarithmic strain space uses structures of the free volume flow theory, which provides a highly predictive modeling capacity at the onset of viscoplastic flow. The integration of this micromechanically motivated approach into a three-dimensional computational model is a key concern of this work. We outline details of the numerical implementation of this model, including elements such as geometric pre- and post-transformations to/from the logarithmic strain space, a thermomechanical operator split algorithm consisting of an isothermal mechanical predictor followed by a heat conduction corrector and finally, the consistent linearization of the local update algorithm for the dissipative variables as well as its relationship to the global tangent operator. The performance of the proposed formulation is demonstrated by means of a spectrum of numerical examples, which we compare with our experimental findings.     

Selective preconcentration of Lanthanum(III) by Coriolus versicolor immobilised on Amberlite XAD-4 and its determination by ICP-OES

Coriolus versicolor, a wood fungus, was immobilised on Amberlite XAD-4 and used as solid-phase biosorbent for preconcentrations of rare earth elements. La(III), Th(IV), U(IV) and Ce(III) were subjected to solid-phase extraction procedure. We observed that La(III) was selectively preconcentrated, while other ions remained in solution at pH 6.0. 5.0 mL of 1.0 mol L^?1 HCl was used to elaute La(III) from column. 250 mg of C. versicolor loaded on 1000 mg of XAD-4 was optimised as solid-phase matrix. Concentrations of ions in solutions were determined by inductively coupled plasma– optical emission spectrometry (ICP-OES). The calibration plot after preconcentration was linear in the range from 1.0 to 50.0 ng mL^?1 for La(III). Limit of detection was found as 0.27 ng mL^?1 for La(III) by SPE method. Relative standard deviation was found lower than 6.7% for 1.0 ng mL^?1 of La(III) solution (n = 10). The sensitivity of ICP-OES was improved by a factor of 46.8. The applicability of the method was validated through the analysis of certified reference samples of tea (NCS ZC-73014) and spinach (NCS ZC-73013).     

Binding of novel fullerene inhibitors to HIV-1 protease: insight through molecular dynamics and molecular mechanics Poisson–Boltzmann surface area calculations

The objectives of this study include the design of a series of novel fullerene-based inhibitors for HIV-1 protease (HIV-1 PR), by employing two strategies that can also be applied to the design of inhibitors for any other target. Additionally, the interactions which contribute to the observed exceptionally high binding free energies were analyzed. In particular, we investigated: (1) hydrogen bonding (H-bond) interactions between specific fullerene derivatives and the protease, (2) the regions of HIV-1 PR that play a significant role in binding, (3) protease changes upon binding and (4) various contributions to the binding free energy, in order to identify the most significant of them. This study has been performed by employing a docking technique, two 3D-QSAR models, molecular dynamics (MD) simulations and the molecular mechanics Poisson–Boltzmann surface area (MM–PBSA) method. Our computed binding free energies are in satisfactory agreement with the experimental results. The suitability of specific fullerene derivatives as drug candidates was further enhanced, after ADMET (absorption, distribution, metabolism, excretion and toxicity) properties have been estimated to be promising. The outcomes of this study revealed important protein–ligand interaction patterns that may lead towards the development of novel, potent HIV-1 PR inhibitors.     

Carbon nanotube-chitosan modified disposable pencil graphite electrode for vitamin B12 analysis

A single walled carbon nanotube-chitosan (SWCNT-chitosan) modified disposable pencil graphite electrode (PGE) was used in this study for the electrochemical detection of Vitamin B(12). Electrochemical behaviors of SWCNT-chitosan PGE and chitosan modified PGE were compared by using cyclic voltammetry (CV), square-wave voltammetry (SWV) and electrochemical impedance spectroscopy (EIS) techniques. SWCNT-chitosan modified electrode was also used for the quantification of Vitamin B(12) in pharmaceutical products. The results show that this electrode system is suitable for sensitive Vitamin B(12) analysis giving good recovery results. The surface morphologies of the SWCNT-chitosan PGE, chitosan modified PGE and unmodified PGE were characterized by using scanning electron microscopy (SEM).